Dimethylformamide → 2,6-Dimethyl-4-nitrobenzenethiol

HRID 1075619Notes

Reaction equation

HRID 1075619 reaction equation
[H-].[Na+].[C:3](OCC)(=[S:5])[CH3:4].FC(F)(F)S(O[C:15]1[C:20](C)=C[CH:18]=[C:17]([N+:22]([O-:24])=[O:23])[C:16]=1C)(=O)=O.[CH3:28]N(C=O)C>>[CH3:20][C:15]1[CH:16]=[C:17]([N+:22]([O-:24])=[O:23])[CH:18]=[C:4]([CH3:28])[C:3]=1[SH:5]

Participants

5

Reactant 4

HCID 6228Dimethylformamide2×HCID 24758Sodium hydrideHCID 136711Thioacetic acid, O-ethyl esterHCID 539044022,6-Dimethyl-3-nitro-phenyl trifluoromethanesulfonate

Product 1

HCID 543703402,6-Dimethyl-4-nitrobenzenethiolYield 60%

Procedure

To a stirred suspension of 570 mg (60% in oil) (14.2 mmol) of sodium hydride in 9 mL of DMF under atmospheric nitrogen at 0° C. was added dropwise 1.64 mL of ethyl thioacetate. After stirring at room temperature for 1 h, it was cooled to 0° C. A solution of 2 g (7.5 mmol) of 2,6-dimethyl-3-nitro-phenyl trifluoromethanesulfonate in 6 mL of DMF was introduced. After stirring at-0° C. for 20 min. it was partitioned between ethyl ether and 3N HCl. The combined organic extracts were washed with brine, dried over MgSO4, filtered and evaporated under reduced pressure. The resulting residue was purified by chromatography using 5% ethyl acetate: hexanes to provide 1.2 g (60%) of 2,6-dimethyl-4-nitro-thiophenol. 1H NMR (CDCl3): 2.43 (s, 3H), 3.67 (s, 1H), 7.93 (s, 2H).

Workup

  1. temperatureit was cooled to 0° C
  2. stirringAfter stirring at-0° C. for 20 min. it
  3. customwas partitioned between ethyl ether and 3N HCl
  4. washThe combined organic extracts were washed with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customevaporated under reduced pressure
  8. customThe resulting residue was purified by chromatography

Sources & evidence

ORD record
ord-7452edbfd95e4e8396bf18a34f32d2a8
Source dataset
uspto-grants-1999_05
Patent number
US05905068

Reaction notes

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